Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/26—Di-epoxy compounds heterocyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5026—Amines cycloaliphatic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the main subject of the present invention is a process for producing a bis-anhydrohexitol ether composition and in particular an isohexide glycidyl ether composition, one of the originalities of which is based on azeotropic distillation carried out under reduced pressure.
• Such compositions, products are used to produce epoxy resins, the function thereof being to form a three-dimensional macromolecular network.
• the compositions obtained according to the process which is the subject of the invention are rich in diepoxy derivatives of isosorbide to the detriment of monoepoxy derivatives, only the first participating in the formation of the three-dimensional network.
• the crosslinking density is therefore increased, thereby making it possible to obtain a material which is more chemically resistant and mechanically stronger and which has a higher glass transition temperature (Tg), compared with the same materials obtained with the bis-anhydrohexitol ethers according to the prior art.
• a subject of the present invention is also the bis-anhydrohexitol ether compositions thus produced, and also the use thereof in the production of composite materials, of coatings or else of adhesives.
• the bisphenol A glycidyl ether (BADGE or DGEBA), of formula (I), is a chemical compound used as a crosslinking agent in the production of epoxy resins.
• This product today appears on the list of carcinogens of group 3 of the IARC (International Agency for Research on Cancer), i.e. it is a substance that is unclassifiable with regard to its carcinogenicity for humans.
• DGEBA is in particular used as an additive in coatings for some cans of food. Free DGEBA can therefore be found in the content of these cans, thereby feeding numerous questions regarding its carcinogenicity (“Determination of Bisphenol A diglycidyl ether and its hydrolysis products in canned oily foods from the Austrian market”, Z. Lebensm, Unters. Forsch. A 208 (1999) pp. 208-211).
• WO 2008/147473 teaches another route, which is a 2-step process, the first consisting in reacting isohexitol with epichlorohydrin in the presence of boron trifluoride, then in adding an alkaline solution (example 3 of this document). Nevertheless, it is known that boron trifluoride is a colorless toxic gas which reacts with moist air to form white fumes composed of hydrogen fluoride, of boric acid and of fluoroboric acid.
• oligomer (III) in order to obtain a three-dimensional network having a higher crosslinking density.
• n the greater the distance between 2 reactive functions and therefore the greater the distance between each crosslinking node.
• a high node density makes it possible to obtain a material which has a higher glass transition temperature (Tg) and which is more chemically resistant and mechanically stronger.
• oligomers and/or of monoglycidyl ethers of isosorbide can be directly related to the epoxy equivalent weight, defined as the weight of resin containing one equivalent of glycidyl function.
• epoxy equivalent weight defined as the weight of resin containing one equivalent of glycidyl function.
• isosorbide diglycidyl ether (figure II) which has a molecular weight of 258 g/mol and which contains 2 glycidyl functions has an epoxy equivalent of 129 g/eq.
• the process for producing a bis-anhydrohexitol ether composition which is the subject of the present application, comprises the following steps:
• step a therefore consists in bringing a dianhydrohexitol into contact with an organic halide.
• the dianhydrohexitol is preferentially an isohexitol, more preferentially chosen from isosorbide, isomannide and isoidide, and is, more preferentially, isosorbide.
• the organic halide is preferentially chosen from epibromohydrin, epifluorohydrin, epiiodohydrin and epichlorohydrin, and is, more preferentially, epichlorohydrin.
• This organic halide is preferentially introduced in excess relative to the hydroxyl functions of the dianhydrohexitol.
• dianhydrohexitol between 2 and 10 mol of organic halide and more preferentially approximately 5 mol will preferentially be introduced.
• step a This first step of bringing a dianhydrohexitol into contact with an organic halide (step a) is carried out in any device well known to those skilled in the art, which makes it possible to bring 2 chemical reagents into contact, and which is equipped with heating and stirring members. It may, for example, be a jacketed reactor.
• the device in question must also be equipped with a member which makes it possible to produce a partial vacuum and with a member which makes it possible to perform an azeotropic distillation, such as a reverse Dean-Stark apparatus surmounted by a condenser.
• step b a partial vacuum is then produced in the device by means of a vacuum pump, the corresponding negative pressure being between 100 mbar and 1000 mbar (step b).
• the pressure in the reaction medium is equal to the difference between atmospheric pressure (1013 mbar) and the pressure claimed (between 100 mbar and 1000 mbar), i.e. a pressure of between 13 mbar and 913 mbar.
• step b) is carried out in such a way as to obtain a negative pressure of between 100 and 800 mbar, in particular between 100 and 600 mbar.
• step c the mixture between the dianhydrohexitol and the organic halide is heated at a temperature of between 50° C. and 120° C.
• the temperature of the heat-transfer fluid circulating in the jacket of the reactor must be regulated in such a way as to be at least equal to the boiling point of the organic halide used, in such a way as to begin the azeotropic distillation.
• said distillation involves only the organic halide: in other words, only a part of the organic halide is eliminated by distillation.
• the boiling point that must be taken into account is the boiling point of the organic halide under the partial pressure which reigns in the device.
• epichlorohydrin has a boiling point of 116° C. at atmospheric pressure, this boiling point being approximately equal to 80° C. under a partial vacuum of 275 mbar.
• the temperature used will be a temperature slightly above (approximately 3° C. above) the boiling point for the organic halide under consideration and for the negative pressure imposed.
• step d a basic reagent is then added to the dianhydrohexitol/organic halide mixture, for a period of between 1 hour and 10 hours.
• the amount of basic reagent is preferentially the stoichiometric amount relative to the number of hydroxyl functions of the dianhydrohexitol (for example: 2 mol of sodium hydroxide for 1 mol of isosorbide). It may nevertheless be chosen to use a slight excess relative to this stoichiometry.
• the basic reagent is chosen from lithium hydroxide, potassium hydroxide, calcium hydroxide and sodium hydroxide optionally in the form of an aqueous solution, and is, very preferentially, an aqueous solution of sodium hydroxide.
• step d As soon as the basic reagent is introduced (step d), there is formation of water by reaction between the dianhydrohexitol and the organic halide, just as there may be provision of additional water by introduction of the basic reagent in the form of an aqueous solution.
• the distillation then involves the mixture of water and organic halide, the first being eliminated and the second returning to the reaction medium.
• the water constitutes the upper phase which is eliminated, whereas the halide in the lower part is returned to the reaction medium.
• the azeotropic distillation is continued until complete elimination of the water.
• the reaction medium is heated for a further period of between 30 minutes and 1 hour after the end of the addition of the basic reagent.
• a phase-transfer catalyst is added during the first step (step a). An even more substantial increase in the fluidity of the products produced is thus achieved, while at the same time maintaining a very high proportion of diepoxy derivatives of isosorbide relative to monoepoxy derivatives of isosorbide.
• the phase-transfer catalyst is preferentially chosen from tetraalkylammonium halides, sulfates or hydrogen sulfates and more preferentially from tetrabutylammonium bromide and tetrabutylammonium iodide.
• the amount of phase-transfer catalyst is between 0.01% and 5%, preferentially between 0.1% and 2%, more preferentially 1% by weight relative to the dianhydrohexitol. A very notable reduction in the epoxy index is then achieved, thereby meaning that the amount of oligomers in the medium is greatly reduced.
• the reaction medium is filtered in order to eliminate the salts formed during the reaction between the halide and the dianhydrohexitol, such as sodium chloride in the case of epichlorohydrin.
• the salts thus recovered are washed once again with epichlorohydrin.
• the washing waters are added to the first filtrate and then concentrated in such a way as to eliminate in particular the epichlorohydrin.
• the concentrating step is carried out for example by vacuum distillation, for example in a device of rotary evaporator and/or scraped film evaporator type. During this concentrating step, the crude product or bis-anhydrohexitol ether composition is gradually heated to 140° C. and the pressure is decreased to 1 mbar.
• an additional step of purification by distillation under reduced pressure can be carried out by means of a scraped-surface exchanger in order to separate the oligomers from the dianhydrohexitol diglycidyl ether. This step is distinct from that described in the previous paragraph.
• Another subject of the present invention is based on the compositions that can be obtained according to the process of the invention.
• a final subject of the present invention is based on the use of these compositions for producing composite materials, coatings and adhesives.
• compositions can also be used for the synthesis of vinyl ester by reaction with (meth)acrylic acids.
• photo-crosslinkable monomers (vinyl esters) may then be used for the production of dental resins, boat hulls and specialty coatings.
• compositions according to the invention can be used in polycondensation reactions in order to obtain a three-dimensional network and a thermorigid material.
• curing agents or crosslinking agents such as amines, polyetheramines, polyamides, amidoamines, Mannich bases, anhydrides, polycarboxylic polyesters, mercaptans, phenolic resins, melamine resins, urea and phenol-formaldehyde.
• Catalysts of Lewis acid, tertiary amine or imidazole type can also be added to the formulation in order to initiate and/or accelerate crosslinking.
• the crosslinking reactions will be carried out at a temperature ranging from 5° to 260° C.
• the materials, resins obtained from the bis-anhydrohexitol ether compositions, which are the subject of the present invention, are more chemically resistant and mechanically stronger and also have a higher glass transition temperature (Tg), compared with the same materials obtained with the bis-anhydrohexitol ethers according to the prior art, as demonstrated hereinafter.
• Tg glass transition temperature
• Isosorbide PolysorbTM P product sold by the company Roquette FrIER
• Trimethylammonium bromide sold by the company Sigma-Aldrich
• tests 1 to 6 were carried out, during which the isosorbide and the epichlorohydrin were reacted, with the addition of an aqueous solution of sodium hydroxide, the azeotropic distillation being carried out at atmospheric pressure.
• test No. 1 the process for test No. 1 was carried out as below.
• reaction medium is filtered under vacuum in order to eliminate therefrom the sodium chloride formed over time.
• the salts are finally washed with epichlorohydrin which is then eliminated by evaporation under reduced pressure in a rotary evaporator.
• the isosorbide diglycidyl ether composition or the composition containing predominantly isosorbide diglycidyl ether is then obtained in the form of a clear and slightly colored liquid (Brookfield viscosity at 25° C. of 19 800 mPa ⁇ s), having an epoxy equivalent of 216 g/equivalent.
• Table 1 summarizes the operating conditions, and in particular:
• This table also indicates the distribution, determined by gas chromatography (GC) (as % of surface area), of the various constituents of the final product/of the final composition.
• GC gas chromatography
• the GC analysis was carried out on a DB1 capillary column (30 m ⁇ 0.32 mm), film thickness of 0.25 ⁇ m).
• the quantification of the species consists in calculating the relative proportion of the areas of the peaks of the chromatogram, the % of each species (x) being equal to the area of the peak of the species (x) divided by the sum of the area of all the peaks.
• tests 7 to 10 4 tests according to the invention (tests 7 to 10) were carried out, during which the isosorbide and the epichlorohydrin were reacted, with the addition of an aqueous solution of sodium hydroxide, the azeotropic distillation being carried out under a partial vacuum.
• the system is brought to a pressure of 568 mbar relative.
• the addition lasts for a total of 3 h 5 min.
• the water is continuously eliminated by azeotropic distillation.
• reaction medium is filtered under vacuum in order to remove therefrom the sodium chloride formed over time.
• the salts are washed with epichlorohydrin which is then eliminated by evaporation under reduced pressure in a rotary evaporator.
• the isosorbide diglycidyl ether composition or the composition containing predominantly isosorbide diglycidyl ether is then obtained in the form of a clear liquid (Brookfield viscosity at 25° C. of 13 900 mPa ⁇ s), having an epoxy equivalent of 200 g/equivalent.
• Example 3 Tests According to the Invention with the Use of a Phase-Transfer Catalyst
• test 11 to 16 6 other tests according to the invention (tests 11 to 16) were carried out, during which the isosorbide and the epichlorohydrin were reacted in the presence of a phase-transfer catalyst, with the addition of an aqueous solution of sodium hydroxide, the azeotropic distillation being carried out under a partial vacuum.
• the system is brought to a pressure of 275 mbar relative.
• the water is then continuously eliminated by azeotropic distillation.
• reaction medium is filtered under vacuum in order to eliminate therefrom the sodium chloride formed over time and the catalyst.
• the salts are washed with epichlorohydrin which is then eliminated by evaporation under reduced pressure in a rotary evaporator.
• the isosorbide diglycidyl ether composition or the composition containing predominantly isosorbide diglycidyl ether is then obtained in the form of a clear liquid (Brookfield viscosity at 25° C. of 4350 mPa ⁇ s) having an epoxy equivalent of 176 g/equivalent.
• Table 2 summarizes the operating conditions used for tests 7 to 16, and in particular:
• This table also indicates the distribution, determined by GC (as % of surface area), of the various constituents of the final product.
• Epoxy resins were prepared from the isosorbide glycidyl ether compositions and in the presence of a curing agent of amine type (isophorone diamine).
• the amount of isophorone diamine introduced is calculated in such a way that the ratio of the number of —NH groups to the number of epoxy groups is equal to 1.
• the isophorone diamine is available under the brand name Vestamid® IPD from Evonik.
• the —NH group weight equivalent is 42.5 g/eq.
• the formula used to calculate the uses of diamine is the following:
• a material which is solid at ambient temperature and which has a glass transition temperature (Tg) of 66° C. is then obtained.
• the glass transition temperature is measured by DSC at the second passage of a temperature ramp of ⁇ 100 to 200° C. at 10° C./min.
• Table 3 summarizes the results obtained according to the isosorbide glycidyl ether compositions used.

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• 2014
  • 2014-01-21 FR FR1450474A patent/FR3016631B1/fr active Active
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